Ligand-Stabilized ZnO Quantum Dots: Molecular Dynamics and Experimental Study

Different aminoalcohol ligands, monoethanolamine (MEA), diethanolamine (DEA) and triethanolamine (TEA) were employed to passivate the surface of ZnO quantum dots (ZnO QDs). High-resolution transmission electron microscopy (HRTEM) imaging revealed that the higher branched aminoalcohols produced smaller sized ZnO QDs. The average size for ZnO/MEA, ZnO/DEA, and ZnO/TEA were found to be 3.2, 2.9, and 2.4 nm. TEA ligands were effective in producing stable, monodisperse ZnO QDs compared with DEA and MEA ligands. Molecular dynamics and semi-empirical calculations suggested that TEA and DEA ligands interact strongly with the partial charge of ZnO dangling bonds and have a large molar volume to hinder the diffusion of precursors through the ligands to the surface of ZnO resulting in a smaller particle size as compared with MEA ligands. As the size of ZnO QDs decreases from ZnO/MEA to ZnO/TEA, the absorption edge and emission peak maximum blue-shifts to a shorter wavelength due to the quantum size effect. The bandgap of ZnO/MEA, ZnO/DEA, and ZnO/TEA was determined to be 3.97, 4.07, and 4.23 eV, and the emission peak was found to be 472, 464, and 458 nm when excited using a 325 nm excitation wavelength, respectively.